U.S. patent number 3,674,758 [Application Number 04/717,926] was granted by the patent office on 1972-07-04 for stabilized tetrafluoroethylene-fluoroolefin copolymers having methyl ester end-groups and process for producing same.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Dana Peter Carlson.
United States Patent |
3,674,758 |
Carlson |
July 4, 1972 |
STABILIZED TETRAFLUOROETHYLENE-FLUOROOLEFIN COPOLYMERS HAVING
METHYL ESTER END-GROUPS AND PROCESS FOR PRODUCING SAME
Abstract
Stabilized tetrafluoroethylene-fluoroolefin copolymers having
methyl ester end-groups are produced from
tetrafluoroethylene-fluoroolefin copolymers having carboxylic acid
end-groups and acid fluoride end-groups by contacting the polymer
with methanol at from about 65-200.degree. C. for the carboxylic
acid end-groups and from about 0-200.degree. C. for the acid
fluoride end-groups and then drying the stabilized polymer.
Inventors: |
Carlson; Dana Peter
(Wilmington, DE) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
24884068 |
Appl.
No.: |
04/717,926 |
Filed: |
April 1, 1968 |
Current U.S.
Class: |
525/326.2;
525/384; 526/247 |
Current CPC
Class: |
C08F
8/14 (20130101); C08F 214/18 (20130101); C08F
8/14 (20130101); C08F 2810/40 (20130101) |
Current International
Class: |
C08F
8/14 (20060101); C08F 8/00 (20060101); C08f
015/06 () |
Field of
Search: |
;260/87.5A |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Donahue, Jr.; J. A.
Claims
What is claimed is:
1. A solid, stable, melt-fabricable copolymer of
tetrafluoroethylene monomer and at least one fluoroolefin monomer
selected from the group of fluoroolefins having the general
formula
XCF.sub.2 (CF.sub.2).sub.n CF .dbd. CF.sub.2
where X = F or H and n = 0 - 9, fluorovinyl ethers having the
general formula
XCF.sub.2 (CF.sub.2).sub.n OCF .dbd. CF.sub.2
where X = F or H and n = 0 - 7, fluorovinyl polyethers having the
general formula
where X = F or H and n = 0 - 7, and
perfluoro(2-methylene-4-methyl-1,3-dioxolane), said copolymer
having acidic end-groups of which at least half have been converted
from the original acidic end-groups to end-groups of the
formula
as measured by infrared analysis and a volatiles index of less than
25.
2. The product of claim 1 in which the fluoroolefin monomer is
hexafluoropropylene.
3. The product of claim 1 in which the fluoroolefin monomer is
perfluoromethyl perfluorovinyl ether.
4. The product of claim 1 in which the fluoroolefin monomer is
perfluoroethyl perfluorovinyl ether.
5. The product of claim 1 in which the fluoroolefin monomer is
perfluoropropyl perfluorovinyl ether.
Description
In general, fluorocarbon copolymers are known to have outstanding
thermal stability. However, certain copolymers of
tetrafluoroethylene (TFE) have a certain amount of instability
introduced into the polymer by the initiation and termination steps
of the polymerization. Both the initiation and termination of the
chain can result in unstable end-groups, such as carboxylic acid
end-groups and acid fluoride end-groups which on storage can be
converted into carboxylic acid end-groups. During melt extrusion
carboxylic acid groups degrade and form gases which become bubbles
in the polymer.
These unstable carboxylic acid and acid fluoride end-groups can be
stabilized by a high-temperature humid heat-treatment process as
disclosed in U. S. Pat. No. 3,085,083, entitled Stabilized
Tetrafluoroethylene-Fluoroolefin Copolymers Having CF.sub.2 H
End-Groups. The main disadvantages of the humid heat-treatment
process are that it is very expensive and adds considerable cost to
polymers that are treated in this manner and also tends to add or
allow contamination of the polymer with dust and other particles
which may be introduced in the heat-treatment process.
SUMMARY OF THE INVENTION
Methyl ester end-groups are easily formed on TFE copolymers having
carboxylic acid end-groups or acid fluoride end-groups by mixing
small amounts of methanol with the polymer at from about 65.degree.
- 200.degree. C. for the carboxylic acid end-groups or at from
about 0.degree. - 200.degree. C. for the acid fluoride end-groups.
The ester end-groups are quite stable under prolonged storage at
extrusion temperatures. No disadvantages were introduced by these
ester end-groups. For example, the electrical properties of
polymers containing a large number of methyl ester end-groups were
found to be equivalent to polymers containing stable end-groups
such as --CF.sub.2 H.
Tetrafluoroethylene copolymers produced by non-aqueous dispersion
polymerization methods having acid fluoride end-groups can be
effectively stabilized by a process which comprises the steps
of:
A. CONTACTING SAID COPOLYMERS WITH METHYL ALCOHOL AT TEMPERATURES
FROM ABOUT 0.degree. C. to about 200.degree. C.; and
B. RECOVERING THE METHYL ESTER OF THE TETRAFLUORO-ETHYLENE
COPOLYMER.
When the tetrafluoroethylene copolymers are produced by aqueous
dispersion methods and have carboxylic acid end-groups as a result
thereof, the acid end-groups can be stabilized in the same manner
as above with methyl alcohol but the temperatures of step (a) must
be from about 65.degree. C. to about 200.degree. C.
The resins this process is applicable upon are any of the resins
produced by an aqueous process which results in the polymer having
carboxylic acid end-groups. Examples of such resins include
copolymers of TFE with hexafluoropropylene (HFP) or perfluoroalkyl
perfluorovinyl ethers which are prepared in an aqueous media with
persulfate initiators. Also, resins such as
tetrafluoroethylene/perfluoroalkyl perfluorovinyl ether copolymers
produced in a non-aqueous media and which contain acid fluoride
end-groups, can be esterified by this process.
Preferred resins this process is applicable on are the copolymers
of tetrafluoroethylene monomer and at least one monomer selected
from the class of monomers consisting of: fluoroolefins having the
general formula
XCF.sub.2 (CF.sub.2).sub.n CF .dbd. CF.sub.2
where X = F or H and n = 0 - 9 such as hexafluoropropylene,
perfluoropentene-1, and 8 hydroperfluorooctene-1; fluorovinyl
ethers having the general formula
XCF.sub.2 (CF.sub.2).sub.n OCF .dbd. CF.sub.2
where X = F or H and n = 0 - 7 such as perfluoromethyl
perfluorovinyl ether, perfluoroethyl perfluorovinyl ether,
perfluoropropyl perfluorovinyl ether, and 3-hydroperfluoropropyl
perfluorovinyl ether; fluorovinyl polyethers having the general
formula
where X = F or H and n = 0 - 7; and
perfluoro(2-methylene-4-methyl-1,3-dioxolane) prepared in either
aqueous or non-aqueous media.
A wide range of reaction conditions are effective to produce the
desired ester. In general higher temperatures and higher pressures
are best for quick esterification of polymers with carboxylic acid
end-groups. Polymers with acid fluoride end-groups can normally be
esterified by contacting the polymer with methanol at room
temperature.
The preferred temperature range for esterifying copolymers having
acid fluoride (--COF) end-groups is from about 20.degree. C. to
about 65.degree. C. The preferred temperature range for esterifying
copolymers having carboxylic acid (--COOH) end-groups is from about
130.degree. C. to about 200.degree. C. The temperature range is
necessary because the aqueously produced copolymers containing
carboxylic acid end-groups are more difficult to esterify and thus
require more strenuous heating than do the non-aqueously produced
copolymers containing acid fluoride end-groups.
The process is operable either by making a slurry of the copolymer
of TFE in liquid methanol or by vapor contacting the copolymer with
methanol. In addition, with non-aqueous copolymers of TFE, the
process is operable by adding methanol to the slurry of the
copolymer with the solvent in which it was formed. It is preferred
that the copolymer be allowed to remain in contact with the
methanol until at least half of the acidic end groups of the
copolymer have been converted to methyl ester end groups.
Methanol is the preferred reagent for forming the methyl ester of
the TFE copolymer but other reagents such as trimethyl orthoformate
or trimethyl orthoacetate can be used to carry out the
esterification. Methanol is the preferred reagent because of its
ready availability and low cost. The esterifying reagent should be
in molar excess to force the reaction to go toward the production
of the ester of the TFE copolymer.
The existence and quantity of certain end-groups in the polymer
were determined by the infrared spectrum generally obtained on
compression molded films of about 10 mils thickness. The end-groups
of interest were found to absorb at 1883 cm..sup..sup.-1, 1814
cm..sup..sup.-1, 1800 cm..sup..sup.-1, 1793 cm..sup..sup.-1 and
1781 cm..sup..sup.-1. The 1883 cm..sup..sup.-1 band measures the
acid fluoride group (--COF) in the polymer. The 1814 and 1781
cm..sup..sup.-1 bands measure the free and bonded forms,
respectively, of the carboxylic acid groups (--COOH). The 1,800
cm..sup..sup.-1 band measures the methyl ester group
(--COOCH.sub.3) and the 1793 cm..sup..sup.-1 band measures the
vinyl end-group (--CF.dbd.CF.sub.2). The quantitative measurement
of the number of these groups was obtained by the measurement of
the extinction coefficients of each of these groups from model
compounds and transferring these coefficients to the measurements
obtained on the polymer. Because of the overlapping of some of the
bands it was found necessary to correct the absorbances for
contributions from several groups. The end-groups are expressed as
the number per one million carbon atoms in the polymer.
The stability of a fluorocarbon polymer during melt fabrication may
be measured by a number of tests. A preferred test comprises the
measurement of the change in melt viscosity when the polymer is
exposed for a period of time to high temperatures, either in the
presence or absence of oxygen. The term "specific melt viscosity"
as used herein means the apparent melt viscosity as measured at
380.degree. C. under a shear stress of 6.5 pounds per square inch.
Specific melt viscosity is determined by using a melt indexer of
the type described in ASTM D-1238-52-T, modified for corrosion
resistance to embody a cylinder, orifice, and a piston made of
Stellite cobalt-chromium-tungsten alloy. The resin is charged to
the 0.375 inch I. D. cylinder which is held at 380.degree. C. .+-.
0.5.degree. C. allowed to come to an equilibrium temperature during
5 minutes, and extruded through the 0.0825 inch diameter, 0.315
inch long orifice under a piston loading of 5,000 grams. The
specific melt viscosity in poises is calculated at 53,150 divided
by the observed extrusion rate in grams per minute. The stability
of the polymer may also be measured by the volatiles index. In this
test, a 10 g. sample of the resin is placed in an aluminum foil
thimble, which is charged into a glass vial attached to a vacuum
system. The vial is evacuated to 2 mm. (Hg) and then on reaching an
equilibrium, placed in a hot block maintained at 380.degree. C. The
change in pressure is recorded every ten minutes over a period of
60 minutes. The volatiles index is calculated by the following
equation
where P.sub.40 and P.sub.0 are the pressures of the sample in mm.
prior to insertion and after 40 min. in the hot block and V is the
volume of the vial.
It is preferred that the volatiles index be less than 25 because
above a volatiles index of 25 the amount of bubbles formed on
extrusion are detrimental to the resins properties.
The following examples will better illustrate the nature of the
present invention; however, the invention is not intended to be
limited to these examples. Parts are by weight unless otherwise
indicated.
EXAMPLE I
Into a conventional one-liter stainless steel agitated pressure
vessel were charged 850 ml. of 1,2,2-trichloro 1,1,2-trifluroethane
("Freon"-113 or F-113), 14 grams of perfluoropropyl/perfluorovinyl
ether (PPVE) and 20 ml. of a 0.027 gram/cc. solution of
bis(perfluoropropionyl) peroxide (3P) in F-113. The pressure was
maintained at 30 psig. during the polymerization run by continuous
addition of tetrafluoroethylene (TFE). The temperature was
controlled at 50.degree. C. by circulating water in the jacket of
the autoclave and conventional control elements. After 20 minutes
the polymer suspension was removed, mixed with 750 ml. of methanol
and filtered through a fritted glass funnel. The gelatinous filter
cake was washed with 500 ml. of methanol in an Osterizer blender
and filtered. This procedure was repeated three times. The polymer
was then dried for 16 hours at 130.degree. C. in an air circulating
oven. A similar polymerization run was made in which the polymer
was not treated with methanol but was filtered and dried as above.
Both the methyl ester capped polymer and the uncapped polymer were
boiled in water for 4 hours and 16 hours and the end-groups and
volatiles indices were measured as described above and compared.
The methyl ester capped polymer maintained a low volatiles index
(less than 25) throughout the test, while that of the uncapped
polymer markedly increased (to approximately 39). The number of
methyl ester end-groups of the methyl ester capped polymer was
virtually unchanged after being boiled for 16 hours.
EXAMPLE II
A polymer was prepared similarly to that in Example I except that a
one-gallon autoclave and larger amounts of starting material, 5,070
grams F-113, 40.1 grams PPVE and 56 ml. of a 0.08 gram/cc. solution
of 3P were used. The vessel was pressured to 30 psig. with TFE and
held at 50.degree. C. To approximately 1 liter of the gel obtained
was added 1 ml. of methanol and the mixture was manually mixed for
several minutes, filtered on a basket centrifuge, and dried at
100.degree. C. for 16 hours. After drying, a small part was
extracted with water in a Soxhlet apparatus for 16 hours and then
dried for 2 hours at 100.degree. C. The volatiles indices of the
methyl ester end capped polymer were low (less than 25). End-group
analysis, by the procedure used in Example I, of the methyl ester
end capped polymer indicated that the ester groups were stable to
the above aging procedure.
EXAMPLE III
To a 180 ml. stainless steel tube was added 15 grams of methyl
ester capped polymer fluff and a 10 ml. film of a methyl ester
capped polymer, prepared as in Example II (with the exception that
only 49 ml. of a 0.057 grams/cc. solution of 3P were used) and 90
ml. of distilled water. The tube was sealed and evacuated to remove
air and then heated to 225.degree. C. for 4 hours. The polymer
fluff and film were recovered and dried 16 hours at 125.degree. C.
The end-groups on the polymer were determined both before and after
the above treatment by infrared analysis as in Example I. Results
indicated that the methyl ester end-groups remained stable during
the treatment.
An uncapped polymer was treated in water for 4 hours at 100.degree.
C. for comparison and its end-groups were analyzed both before and
after treatment. Most of the acid fluoride end-groups were
converted to carboxylic acid end-groups which caused an increase in
the volatiles index.
EXAMPLE IV
The polymer for this Example was prepared as in Example I using
1,340 grams F-113, 10.6 grams PPVE, 0.60 gram 3P initiator in an
autoclave pressured to 30 psig. with TFE. The polymer was then
methyl ester end capped by adding 5 ml. methanol to the dispersion
of the polymer in F-113, stirring, filtering, and drying overnight
at 100.degree. C. A ten-gram sample of the methyl ester capped
polymer was placed in a Pyrex glass tube and inserted into an
aluminum block held at 380.degree. C. A very slight air stream was
blown into the sample tube. After 15 minutes the sample was removed
and weight loss, melt viscosity at 380.degree. C., and the number
and type of end-groups were measured. The treatment was repeated
using 30 and 60 minutes. After 30 minutes the number of methyl
ester end-groups was essentially unchanged. Methyl ester end-groups
were undetectable only after 60 minutes at 380.degree. C. Only
small changes were noted in the weight and melt viscosity of the
sample.
Another sample of similar methyl ester capped polymer was subjected
to oxidative attack by placing it in an air circulating oven at
300.degree. C. The change in melt viscosity was very small after 6
hours. After 4 hours the number of methyl ester end-groups had
decreased only slightly. Methyl ester groups were undetectable only
after 6 hours at 300.degree. C.
EXAMPLE V
Each of several batches of polymer prepared as in Example III, were
treated with 10 ml. of methanol, stirred, centrifuged, treated with
2,500 ml. methanol for 10 minutes, centrifuged and then dried at
125.degree. C. overnight. A blend of the methyl ester capped
polymers was prepared and extruded four times using a 11/2 inch
extruder. The extrusion temPerature was 390.degree. C. The melt
viscosity, volatiles index and end-groups were analyzed before and
after each extrusion. Results indicate that the methyl ester
end-groups were stable under the conditions of extrusion. Melt
viscosity did not change appreciably and the volatiles index
remained below 25.
The polymer used in Examples VI and VII was prepared as in Example
I at Column 4, lines 23-64, in U. S. Pat. No. 2,946,763 issued July
26, 1960 to M. I. Bro et al. It will be referred to as "FEP
polymer" for convenience.
EXAMPLE VI
Twenty grams of FEP polymer, filtered but not dried, were placed in
a stainless steel shaker tube of about 20 ml. total volume. 100 ml.
of reagent grade methanol was added to the shaker tube which was
then sealed and heated to 140.degree. C. for 120 minutes with
agitation. At the end of this heating period the cylinder was
cooled to room temperature and its contents washed several times
with methanol. After air drying the sample until the odor of
methanol was not detectable, the sample was dried at 115.degree. C.
under vacuum overnight. Infrared analysis of films compression
molded at 340.degree. C. showed that 225 methyl ester and 206
perfluorovinyl end-groups per 10.sup.6 carbon atoms were present,
indicating that all carboxylic acid end-groups had been
esterified.
EXAMPLE VII
Twenty grams of dry FEP polymer were placed in a stainless steel
shaker tube of about 200 cc. total volume. 100 ml. of reagent grade
methanol was added to the shaker tube which was then sealed and
heated to 190.degree. C. for 120 minutes with agitation. At the end
of this heating period the cylinder was cooled to room temperature
and its contents washed several times with methanol. After air
drying the sample until the odor of methanol was not detectable,
the sample was dried at 115.degree. C. under vacuum overnight.
Infrared analysis of films compression molded at 340.degree. C.
showed that 329 methyl ester and 15 perfluorovinyl end-groups per
10.sup.6 carbon atoms were present, indicating that all carboxylic
acid end-groups had been esterified.
As many apparently widely different embodiments of this invention
may be made without departing from the spirit or scope thereof, it
is to be understood that this invention is not limited to the
specific embodiments thereof except as defined in the appended
claims.
* * * * *